MgO-A12O3-SiO2-Based Crystallizable Glass and Crystallized Glass, and Manufacturing Method Thereof

ABSTRACT

The invention provides a crystallizable glass, a crystallized glass, and manufacturing methods thereof. The crystallizable glass can be crystallized in a short period of time, and can maintain its glass shape and its surface condition during a crystallization process. The crystallized glass has good mechanical strength, an adequate thermal expansion coefficient that allows the crystallized glass to be used as a construction material, less content of alkali-metal oxides, and good chemical durability. The MgO—Al 2 O 3 —SiO 2 -based crystallizable glass and crystallized glass contain, by mass percent, 55.0-65.0% SiO 2 , 8.0-14.0% Al 2 O 3 , 10.0-20.0% MgO, 1.5-6.0% CaO, 1.0-2.2% Li 2 O, 0.7-3.0% Na 2 O, 2.5-4.0% K 2 O, and 1.5-3.0% F.

CLAIM OF PRIORITY

This application claims the priority benefit of Japanese Application Serial Number JP2009-254932, filed on Nov. 6, 2009. All disclosure of the Japanese application is incorporated herein by reference.

TECHNICAL FIELD

This invention relates to a MgO—Al₂O₃—SiO₂-based crystallizable glass and a MgO—Al₂O₃—SiO₂-based crystallized glass, and the manufacturing methods thereof.

BACKGROUND ART

A crystallized glass, which is used as an exterior and interior decorative material for buildings or used as a surface material for home desks and office desks, is required to have high chemical durability and mechanical strength and it gives a nice appearance at low prices. For such crystallized glass, various crystallized glasses have been proposed.

In one representative example, after a melted glass is shaped into a desired form and becomes a crystallizable glass, the crystallizable glass undergoes a crystallization heating process to form a crystallized glass. At least one or more crystals of K(Li,Al)₃(Al,Si)₄O₁₀(OH,F)₂ (lepidolite), KLiMg₂Si₄O₁₀F₂ (tainiolite), Li₂Al₂Si₃O₁₀, LiAlSi₃O₈, Li_(x)Al_(x)Si_(3-x)O₆ (virgilite), β-LiAlSi₂O₆ (β-spodumene solid solution, Li₂O—Al₂O₃-nSiO₂(n≧4)), Mg₂Al₄Si₅O₁₈ (μ-cordierite), KMg₃(Si₃AlO₁₀)(OH)₂ (phlogopite), and KMgAlSi₄O₁₀(OH)₂ (leucophyllite) can be precipitated from the crystallizable glass as a primary crystal, thereby transforming the crystallizable glass into a crystallized glass, which has good chemical durability and mechanical strength. (For example, refer to Patent Document 1.)

On the other hand, a continuous forming production method using a continuous forming process equipment has served as a manufacturing method for crystallized glass, for example, as described in Patent Document 2. With this production method, the conventional annealing step performed before crystallization can be eliminated, thereby simplifying the manufacturing process, so as to reach the cost reduction goal.

-   Patent Document 1: JP-2007-126299 -   Patent Document 2: JP-2005-041726

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

However, for the crystallized glass disclosed in Patent Document 1, since the thermal expansion coefficient of its primary crystal is not sufficiently large, the crystallized glass may be inadequate to be used as a construction material when the difference between its thermal expansion coefficient and those of other construction materials used with this crystallized glass (such as concrete) is too large.

Furthermore, since the glass matrix of the crystallized glass is prone to soften, flow and deform during the crystallization heating process for transforming a crystallizable glass into a crystallized glass, the continuous forming production method using the continuous forming process equipment disclosed in Patent Document 2 is inadequate to be used.

One object of the invention is to solve various problems in the aforesaid conventional art and reach the following goals.

Specifically, one object of the invention is to provide a crystallizable glass, which can be crystallized in a short period of time, can maintain its glass shape and its surface condition during the crystallization process, and is adequate for the aforesaid continuous forming production method; and a crystallized glass, which has good mechanical strength, adequate thermal expansion coefficient that allows the crystallized glass to be used as a construction material, less content of alkali-metal oxides, and good chemical durability. In addition, another object of the invention is to provide the methods for manufacturing the crystallizable glass and crystallized glass.

Means to Solve the Problems

According to the results obtained by the inventors through diligent studies, it has been found that the following methods of the invention can achieve the aforesaid objects.

The specific means to achieve the aforesaid objects are as follows:

-   (1) A MgO—Al₂O₃—SiO₂-based crystallizable glass, which is     characterized by containing, by mass percent, 55.0-65.0% SiO₂,     8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO, 1.0-2.2% Li₂O,     0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F. -   (2) The MgO—Al₂O₃—SiO₂-based crystallizable glass recited in the     above (1), which is characterized in that lepidolite or a     lithium-containing waste is used as a raw material for the     crystallizable glass, in which an amount of the lepidolite or the     lithium-containing waste is 25-50% by mass of all raw materials used     for the crystallizable glass, and the lepidolite or the     lithium-containing waste contains, by mass percent, 50.0-60.0% SiO₂,     20.0-30.0% Al₂O₃, 0-0.5% MgO, 3.0-5.0% Li₂O, 1.0-3.0% Na₂O, 6.0-9.0%     K₂O, 4.0-6.0% F, 0-0.2% P₂O₅, 1.0-2.0% Rb₂O, 0.1-0.5% Cs₂O, 0.2-0.8%     MnO₂, and 0.1-0.4% Fe₂O₃. -   (3) A MgO—Al₂O₃—SiO₂-based crystallized glass, which is     characterized by containing, by mass percent, 55.0-65.0% SiO₂,     8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO, 1.0-2.2% Li₂O,     0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F. -   (4) The MgO—Al₂O₃—SiO₂-based crystallized glass recited in the above     (3), which is characterized in that lepidolite or a     lithium-containing waste is used as a raw material for the     crystallized glass, in which an amount of the lepidolite or the     lithium-containing waste is 25-50% by mass of all raw materials used     for the crystallized glass, and the lepidolite or the     lithium-containing waste contains, by mass percent, 50.0-60.0% SiO₂,     20.0-30.0% Al₂O₃, 0-0.5% MgO, 3.0-5.0% Li₂O, 1.0-3.0% Na₂O, 6.0-9.0%     K₂O, 4.0-6.0% F, 0-0.2% P₂O₅, 1.0-2.0% Rb₂O, 0.1-0.5% Cs₂O, 0.2-0.8%     MnO₂, and 0.1-0.4% Fe₂O₃. -   (5) The MgO—Al₂O₃—SiO₂-based crystallized glass recited in the     above (3) or (4), which is characterized by comprising at least one     or more crystals of Ca(Mg, Al)(Si, Al)₂O₆(diopside),     MgSiO₃(enstatite), MgSiO₃ (clinoenstatite),     KCa₄Si₈O₂₀(OH).8H₂O(hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀     (lepidolite-3T), K(Si₃Al)O₈(sanidine),     KMg₃(Si₃Al)O₁₀(OH)₂(biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂     (phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂(muscovite-1M). -   (6) The MgO—Al₂O₃—SiO₂-based crystallized glass recited in the above     (5), which is characterized by being obtained by precipitating at     least one or more crystals of Ca(Mg, Al)(Si, Al)₂O₆(diopside),     MgSiO₃(enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O     (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T),     K(Si₃Al)O₈(sanidine), KMg₃(Si₃Al)O₁₀(OH)₂(biotite-1M),     KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), and     KAl₂Si₃AlO₁₀(OH)₂(muscovite-1M) from the MgO—Al₂O₃—SiO₂-based     crystallizable glass recited in the above (1) and (2). -   (7) A method for manufacturing a MgO—Al₂O₃—SiO₂-based crystallizable     glass, which is characterized by comprising a step A, preparing a     mixture of glass raw materials containing, by mass percent,     55.0-65.0% SiO₂, 8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO,     1.0-2.2% Li₂O, 0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F; a step     B, melting the mixture obtained in the step A into a melted glass;     and a step C, shaping the melted glass obtained in the step B. -   (8) The method for manufacturing a MgO—Al₂O₃—SiO₂-based     crystallizable glass recited in the above (7), which is     characterized in that the above step A includes a step A-1, stirring     lepidolite or a lithium-containing waste, wherein the lepidolite or     the lithium-containing waste contains, by mass percent, 50.0-60.0%     SiO₂, 20.0-30.0% Al₂O₃, 0-0.5% MgO, 3.0-5.0% Li₂O, 1.0-3.0% Na₂O,     6.0-9.0% K₂O, 4.0-6.0% F, 0-0.2% P₂O₅, 1.0-2.0% Rb₂O, 0.1-0.5% Cs₂O,     0.2-0.8% MnO₂, and 0.1-0.4% Fe₂O₃; and a step A-2, preparing the     mixture of glass raw materials by mixing, by stirring, the stirred     product obtained in the step A-1 with other glass raw materials,     wherein the stirred product is 20-50% by mass of the mixture of     glass raw materials. -   (9) A method for manufacturing a MgO—Al₂O₃—SiO₂-based crystallized     glass, which is characterized by comprising a step A, preparing a     mixture of glass raw materials containing, by mass percent,     55.0-65.0% SiO₂, 8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO,     1.0-2.2% Li₂O, 0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F; a step     B, melting the mixture obtained in the step A into a melted glass; a     step C, shaping the melted glass obtained in the step B to give a     crystallizable glass; and a step D, performing a crystallization     heating process on the crystallizable glass obtained in the step C. -   (10) The method for manufacturing a MgO—Al₂O₃—SiO₂-based     crystallized glass recited in the above (9), which is characterized     in that the above step A includes a step A-1, stirring lepidolite or     a lithium-containing waste, wherein the lepidolite or the     lithium-containing waste contains, by mass percent, 50.0-60.0% SiO₂,     20.0-30.0% Al₂O₃, 0-0.5% MgO, 3.0-5.0% Li₂O, 1.0-3.0% Na₂O, 6.0-9.0%     K₂O, 4.0-6.0% F, 0-0.2% P₂O₅, 1.0-2.0% Rb₂O, 0.1-0.5% Cs₂O, 0.2-0.8%     MnO₂, and 0.1-0.4% Fe₂O₃; and a step A-2, preparing the mixture of     glass raw materials by mixing, by stirring, the stirred product     obtained in the step A-1 with other glass raw materials, wherein the     stirred product is 20-50% by mass of the mixture of glass raw     materials. -   (11) The method for manufacturing a MgO—Al₂O₃—SiO₂-based     crystallized glass recited in the above (9) or (10), which is     characterized in that the above step D includes precipitating at     least one or more crystals of Ca(Mg,Al)(Si,Al)₂O₆(diopside),     MgSiO₃(enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O     (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T),     K(Si₃Al)O₈(sanidine), KMg₃(Si₃Al)O₁₀(OH)₂(biotite-1M),     KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and     KAl₂Si₃AlO₁₀(OH)₂(muscovite-1M) by performing the crystallization     heating process.

Effect of the Invention

The invention provides a crystallizable glass, which can be crystallized in a short period of time, can maintain its glass shape and its surface condition during the crystallization process, and is adequate for the aforesaid continuous forming production method; and a crystallized glass, which has good mechanical strength, adequate thermal expansion coefficient that allows the crystallized glass to be used as a construction material, less content of alkali-metal oxides, and good chemical durability. Furthermore, the invention also provides the methods of manufacturing the crystallizable glass and crystallized glass.

EMBODIMENTS OF THE INVENTION A. Crystallizable Glass and Crystallized Glass

A crystallizable glass and a crystallized glass according to the invention are characterized by containing, by mass percent, 55.0-65.0% SiO₂, 8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO, 1.0-2.2% Li₂O, 0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F.

The reason regarding defining the above percentage composition for the crystallizable glass and crystallized glass according to the invention is described hereinafter. In the following, “%” indicates “mass percent”, if not otherwise specified.

A content of SiO₂ is 55.0-65.0%, preferably 55.0-60.0%. When the content of SiO₂ is less than 55.0%, the chemical durability of the crystallized glass may be deteriorated, and the glass is prone to deformation during the crystallization heating process. On the other hand, when the content of SiO₂ is more than 65.0%, the melting point of the glass becomes higher, thereby causing possible negative effects upon the production and causing the glass to crack or break during the crystallization heating process.

A content of Al₂O₃ is 8.0-14.0%, preferably 10.0-14.0%. When the content of Al₂O₃ is less than 8.0%, it may become difficult to crystallize the glass. In addition, it is possible to cause the glass to crack or break during the crystallization heating process. On the other hand, when the content of Al₂O₃ is more than 14.0%, it becomes difficult to melt the glass, and the devitrification temperature of the glass may be increased. In addition, it is possible to cause the glass to crack or break during the crystallization heating process.

A content of MgO is 10.0-20.0%, preferably 10.0-15.0%. When the content of MgO is less than 10.0%, the melting point of the glass becomes higher, so that it may become difficult to crystallize the glass, and it may be difficult to precipitate the crystals of MgSiO₃ (enstatite) and MgSiO₃ (clinoenstatite). Furthermore, it becomes difficult to maintain the glass shape while the glass is prone to deformation during the crystallization heating process. In addition, it is possible to cause the glass to crack or break during the crystallization heating process. On the other hand, when the content of MgO is more than 20.0%, the devitrification temperature of the glass may be increased.

A content of CaO is 1.5-6.0%, preferably 2.0-5.0%. When the content of CaO is less than 1.5%, it is difficult to precipitate the crystals of Ca(Mg,Al)(Si,Al)₂O₆(diopside). In addition, it becomes difficult to maintain the glass shape while the glass is prone to deformation during the crystallization heating process. Furthermore, it is possible to cause the glass to crack or break during the crystallization heating process. On the other hand, when the content of CaO is more than 6.0%, it is prone to precipitate crystals other than diopside.

A content of Li₂O is 1.0-2.2%, preferably 1.0-1.8%. Li₂O acts as an effective co-solvent; however, if its content is less than 1.0%, its co-solvent effect becomes weaker and the solubility becomes lower. In addition, flat glass can become poorly formed. Moreover, when its content is less than 1.0%, it is difficult to precipitate the crystals of K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T). On the other hand, when the content of Li₂O is more than 2.2%, it is prone to precipitate β-quartz solid solution or β-spodumene solid solution; however, the resulting crystallized glass may be inadequate to be used as a construction material because the thermal expansion coefficients of these types of crystals are not sufficiently large.

A content of Na₂O is 0.7-3.0%. Na₂O acts as an effective co-solvent; however, if its content is less than 0.7%, its co-solvent effect becomes weaker. If its content is more than 3.0%, it becomes difficult to maintain the glass shape while the glass is prone to deformation during the crystallization heating process. In addition, the chemical durability of the glass can also be deteriorated.

A content of K₂O is 2.5-4.0%. K₂O acts as an effective co-solvent; however, when its content is less than 2.5%, its co-solvent effect becomes weaker. If its content is more than 4.0%, it becomes difficult to maintain the glass shape while the glass is prone to deformation during the crystallization heating process. Furthermore, the chemical durability of the glass can also be deteriorated.

A content of F is 1.5-3.0%. F can facilitate crystallization, and it acts as an effective co-solvent; however, if its content is less than 1.5%, its effect in facilitating crystallization becomes weaker, and its co-solvent effect becomes weaker as well. On the other hand, if the content of F is more than 3.0%, the erosion of refractory lining in the furnace can be intense.

The crystallizable glass according to the invention is capable of being crystallized in a short period of time while maintaining its glass shape and its surface condition during the crystallization due to the aforesaid percentage composition.

Furthermore, as mentioned above, the crystallized glass according to the invention has excellent chemical durability because the total content of alkali-metal oxides, Li₂O, Na₂O, and K₂O, is low.

A crystallizable glass and a crystallized glass according to the invention may also contain BaO, P₂O₅, Rb₂O, Cs₂O, MnO₂, Fe₂O₃ in addition to the aforesaid components.

Preferably, a content of BaO is 0-5.0%. BaO acts as an effective co-solvent; however, if its content is more than 5.0%, it may be difficult to crystallize the glass.

Preferably, contents of P₂O₅, Rb₂O, Cs₂O, MnO₂, Fe₂O₃ are 0-0.2%, 0-0.8%, 0-0.2%, 0-0.3%, 0-0.2%, respectively. These components can be included in a mixture of glass raw materials by using the following lepidolite or lithium-containing waste as a glass raw material.

A crystallizable glass and a crystallized glass according to the invention may contain 1% or less of either As₂O₃ or Sb₂O₃ as a fining agent. Moreover, they may contain 3% or less V₂O₅, Cr₂O₃, MnO₂, Fe₂O₃, CoO, NiO, CuO or the like as a coloring agent.

Perferably, an amount of the lepidolite or the lithium-containing waste used as a glass raw material for the crystallizable glass and crystallized glass according to the invention is 25-50% by mass of the mixture of all glass raw materials used, wherein the lepidolite or the lithium-containing waste contains, by mass percent, 50.0-60.0% SiO₂, 20.0-30.0% Al₂O₃, 0-0.5% MgO, 3.0-5.0% Li₂O, 1.0-3.0% Na₂O, 6.0-9.0% K₂O, 4.0-6.0% F, 0-0.2% P₂O₅, 1.0-2.0% Rb₂O, 0.1-0.5% Cs₂O, 0.2-0.8% MnO₂, and 0.1-0.4% Fe₂O₃.

In the invention, a crystallizable glass and a crystallized glass may contain some or all of SiO₂, Al₂O₃, MgO, Li₂O, Na₂O, K₂O and F by using the aforesaid lepidolite or lithium-containing waste as a glass raw material. Furthermore, the crystallizable glass and crystallized glass may contain P₂O₅, Rb₂O, Cs₂O, MnO₂, and Fe₂O₃.

Preferably, an amount of the aforesaid lepidolite or lithium-containing waste used as a glass raw material is 25-50% by mass of the mixture of glass raw materials. When the amount is more than 50%, it becomes difficult to adjust the composition of the mixture. If the amount is less than 25%, the manufacturing cost may not be effectively reduced.

Preferably, one or more crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) are included as primary crystals for a crystallized glass of the invention.

Since the crystallized glass according to the invention includes at least one type of the above crystals, it has excellent mechanical strength and an adequate thermal expansion coefficient that allows the crystallized glass to be used as a construction material.

The mechanical strength can be evaluated by three-point bending test. Preferably, the bending strength is 500-1000 kg/cm².

As for the thermal expansion coefficient, by taking into consideration its relationship with the thermal expansion coefficients of other construction materials used with the crystallized glass, the thermal expansion coefficient of the glass is preferably between 60×10⁻⁷/° C. to 140×10⁻⁷/° C.

Since a crystallized glass according to the invention has to be crystallized in a short period of time while maintaining its glass shape and its surface condition through the crystallization, it may preferably contain Ca(Mg,Al)(Si,Al)₂O₆(diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), and KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1). More preferably, it may contain Ca(Mg,Al)(Si,Al)₂O₆(diopside), MgSiO₃ (enstatite), and MgSiO₃ (clinoenstatite).

B. Methods of Manufacturing Crystallizable Glass and Crystallized Glass

A method for manufacturing a crystallizable glass according to the invention includes: preparing a mixture of glass raw materials (step A); melting the mixture obtained in step A to give a melted glass (step B); and shaping the melted glass obtained in step B (step C).

Furthermore, a method for manufacturing a crystallized glass according to the invention includes the above three steps and further includes a step of performing a crystallization heating process on a crystallizable glass (step D).

Since the crystallizable glass according to the invention can be crystallized quickly while maintaining its glass shape and its surface condition through the crystallization, it can be used in manufacturing the crystallized glass according to the invention.

In methods of manufacturing a crystallizable glass and a crystallized glass according to the invention, a mixture of glass raw materials containing 55.0-65.0% SiO₂, 8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO, 1.0-2.2% Li₂O, 0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F may be used.

Lepidolite or a lithium-containing waste which contains 50.0-60.0% SiO₂, 20.0-30.0% Al₂O₃, 0-0.5% MgO, 3.0-5.0% Li₂O, 1.0-3.0% Na₂O, 6.0-9.0% K₂O, 4.0-6.0% F, 0-0.2% P₂O₅, 1.0-2.0% Rb₂O, 0.1-0.5% Cs₂O, 0.2-0.8% MnO₂, and 0.1-0.4% Fe₂O₃ can be used in the above mixture. For example, mining wastes from the excavation of rare metals can be used as the aforesaid waste.

Preferably, an amount of the above lepidolite or lithium-containing waste is 25-50% of the mixture of all the glass raw materials used. If the amount is more than 50%, it is difficult to adjust the composition of the mixture. If the amount is less than 25%, the manufacturing cost may not be effectively reduced. It is nice to use lepidolite or a lithium-containing waste in terms of environmental protection.

Each step of the methods for manufacturing a crystallizable glass and a crystallized glass according to the invention is described hereinafter.

Step A is a step of preparing a mixture of glass raw materials containing 55.0-65.0% SiO₂, 8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO, 1.0-2.2% Li₂O, 0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F.

When the above lepidolite or lithium-containing waste is used as a glass raw material, the lepidolite or the lithium-containing waste is stirred (step A-1), and then the stirred product is mixed with other glass raw materials to prepare the mixture of glass raw materials having the aforesaid percentage composition (step A-2).

In addition to the aforesaid components, the mixture of glass raw materials may further contain 0-0.2% P₂O₅, 0-0.8% Rb₂O, 0-0.2% Cs₂O, 0-0.3% MnO₂, and 0-0.2% Fe₂O₃ by using the above lepidolite or lithium-containing waste.

In the step A, an oxide of a transition element, such as V₂O₅, Cr₂O₃, MnO₂, Fe₂O₃, CoO, NiO, CuO, may be added as a coloring agent. As₂O₃ or Sb₂O₃ may be also added as a fining agent.

Step B is a step of melting the mixture obtained in the step A to give a melted glass. For example, a melted glass can be obtained by using conventional methods well known in the art via melting equipment, such as a crucible furnace, a day tank furnace or a tank furnace.

The melting temperature is not limited specifically, but can be 1400-1600° C., preferably 1450-1550° C.

Step C is a step of shaping (or forming) the melted glass obtained in the step B to give a crystallizable glass. The method of shaping the melted glass is not limited specifically, and the shaping methods well known in the art can be used. For example, the glass can be pressed into a band-like glass by a rolling process.

Step D is a step of performing a heating process on the crystallizable glass obtained in the step C, precipitating crystals and enabling the crystals to grow to obtain a crystallized glass. Preferably, at least one or more of Ca(Mg,Al)(Si,Al)₂O₆(diopside), MgSiO₃ (enstatite), MgSiO₃ (lcinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) may be precipitated through the crystallization heating process.

The heating rate, holding temperature and holding time of the crystallization heating process in the step D are not limited specifically, and adequate conditions can be selected to enable the crystals to be precipitated and grow completely. In view of productivity, it is preferable to provide a high heating rate and short holding time.

In a method for manufacturing a crystallized glass according to the invention, an annealing step performed before crystallization is not required. Therefore, a method according to the invention can utilize the continuous forming production method using the continuous forming process equipment disclosed in Japanese Patent Publication No. 2005-041726 to produce a crystallized glass, thereby simplifying the manufacturing process to reduce the cost.

Specifically, in a method for manufacturing a crystallized glass according to the invention using, for example, the continuous forming process equipment for producing a crystallized glass disclosed in the aforesaid Japanese Patent Publication, a mixture of glass raw materials is melted in a melting device; the melted glass flows through a devitrifying-prevention device at a predetermined rate controlled by a viscosity control device and a liquid-level control device. Then the melted glass is introduced into a rolling device to be pressed into a band-like glass. The band-like glass is automatically transferred to a crystallization device directly and continuously, and then crystallized by the crystallization device. The band-like crystallized glass is directly and continuously transferred to a cutting device and then automatically cut into plates of a predetermined length by the cutting device. In other words, in a preferable aspect, the steps from melting the mixture of glass raw materials to cutting the glass can be automatically performed continuously.

A crystallized glass obtained by a method for manufacturing a crystallized glass according to the invention can be used as a construction material and a surface material for furniture after undergoing subsequent processing, such as cutting, polishing, surface processing.

EXAMPLES

The following examples are provided to further illustrate the implementation of the invention. However, the scope of the invention is not limited to the given examples. Moreover, “%” indicates “mass percent”, if not otherwise specified.

Lepidolite or a lithium-containing waste at 25-45% by mass of the mixture of glass raw materials is used in each example of the invention and comparative example to prepare various mixtures of glass raw materials having percentage compositions corresponding to samples recited in Table 1 and Table 2. Although the composition of the lepidolite or lithium-containing waste used may slightly vary between the samples due to acquisition at different times, it essentially includes the following contents.

SiO₂ . . . 53-58% Al₂O₃ . . . 21-26% MgO . . . 0-0.3% Li₂O . . . 3.2-4.6% Na₂O . . . 1.7-2.5% K₂O . . . 7.0-8.8% F . . . 4.2-5.5% P₂O₅ . . . 0.07-0.15% Rb₂O . . . 1.2-1.8% Cs₂O . . . 0.1-0.3% MnO₂ . . . 0.3-0.7% Fe₂O₃ . . . 0.15-0.35% Example 1

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 1 of Table 1, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 650° C. at a rate of 360° C. per hour. After it was kept at 650° C. for 60 minutes, it was heated to 860° C. at a rate of 60° C. per hour. After it was kept at 860° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆(diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂(muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

Example 2

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 2 of Table 1, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 650° C. at a rate of 360° C. per hour. After it was kept at 650° C. for 60 minutes, it was heated to 860° C. at a rate of 30° C. per hour. After it was kept at 860° C. for 60 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

Example 3

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 3 of Table 1, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 360° C. per hour. After it was kept at 700° C. for 60 minutes, it was heated to 860° C. at a rate of 30° C. per hour. After it was kept at 860° C. for 60 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆(diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂(muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

Example 4

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 4 of Table 1, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 360° C. per hour. After it was kept at 700° C. for 30 minutes, it was heated to 860° C. at a rate of 120° C. per hour. After it was kept at 860° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆(diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂(muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

Example 5

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 5 of Table 1, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 360° C. per hour. After it was kept at 700° C. for 30 minutes, it was heated to 900° C. at a rate of 120° C. per hour. After it was kept at 900° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

Example 6

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 6 of Table 1, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 360° C. per hour. After it was kept at 700° C. for 30 minutes, it was heated to 900° C. at a rate of 60° C. per hour. After it was kept at 900° C. for 60 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

Example 7

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 7 of Table 1, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 480° C. per hour. After it was kept at 700° C. for 30 minutes, it was heated to 920° C. at a rate of 120° C. per hour. After it was kept at 920° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆(diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂(biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

Example 8

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 8 of Table 1, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 360° C. per hour. After it was kept at 700° C. for 30 minutes, it was heated to 875° C. at a rate of 120° C. per hour. After it was kept at 875° C. for 60 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂(muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

Example 9

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 9 of Table 1, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 650° C. at a rate of 300° C. per hour. After it was kept at 650° C. for 30 minutes, it was heated to 810° C. at a rate of 120° C. per hour. After it was kept at 810° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆(diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂(muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

Example 10

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 10 of Table 1, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 600° C. per hour. After it was kept at 700° C. for 30 minutes, it was heated to 910° C. at a rate of 120° C. per hour. After it was kept at 910° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

Comparative Example 1

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 11 of Table 2, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 600° C. per hour. After it was kept at 700° C. for 30 minutes, it was heated to 910° C. at a rate of 120° C. per hour. After it was kept at 910° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

However, the glass was deformed during the crystallization heating process. Therefore, it was inadequate to be produced by the continuous forming production method.

Comparative Example 2

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 12 of Table 2, and then added into a crucible. The mixture was melted at 1580° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 300° C. per hour. After it was kept at 700° C. for 60 minutes, it was heated to 880° C. at a rate of 120° C. per hour. After it was kept at 880° C. for 60 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The crystallized glass plate was white.

However, the glass cracked during the crystallization heating process. Therefore, no product was obtained.

Comparative Example 3

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 13 of Table 2, and then added into a crucible. The mixture was melted at 1580° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 300° C. per hour. After it was kept at 700° C. for 30 minutes, it was heated to 860° C. at a rate of 60° C. per hour. After it was kept at 860° C. for 60 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), and KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite) was obtained. The crystallized glass plate was white.

However, the glass cracked during the crystallization heating process. Therefore, no product was obtained.

Comparative Example 4

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 14 of Table 2, and then added into a crucible. The mixture was melted at 1580° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 720° C. at a rate of 300° C. per hour. After it was kept at 720° C. for 30 minutes, it was heated to 980° C. at a rate of 60° C. per hour. After it was kept at 980° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The crystallized glass plate was white.

However, the glass cracked during the crystallization heating process. Therefore, no product was obtained.

Comparative Example 5

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 15 of Table 2, and then added into a crucible. The mixture was melted at 1580° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 720° C. at a rate of 300° C. per hour. After it was kept at 720° C. for 30 minutes, it was heated to 880° C. at a rate of 60° C. per hour. After it was kept at 880° C. for 30 minutes, it was cooled in the furnace.

As a result, most crystals were not precipitated, and the crystallized glass plate was translucent.

Moreover, the glass was deformed and cracked during the crystallization heating process. Therefore, no product was obtained.

Comparative Example 6

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 16 of Table 2, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 650° C. at a rate of 300° C. per hour. After it was kept at 650° C. for 30 minutes, it was heated to 860° C. at a rate of 120° C. per hour. After it was kept at 860° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) and LiAlSi₂O₆(β-spodumene) was obtained. The appearance of the crystallized glass plate was nice and was white.

However, since the crystal of LiAlSi₂O₆(β-spodumene) was precipitated besides the target crystals, the thermal expansion coefficient of the glass becomes lower, thereby the glass was inadequate to be used as a construction material.

Comparative Example 7

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 17 of Table 2, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 650° C. at a rate of 360° C. per hour. After it was kept at 650° C. for 60 minutes, it was heated to 840° C. at a rate of 60° C. per hour. After it was kept at 840° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

However, the glass was deformed during the crystallization heating process. Therefore, it was inadequate to be produced by the continuous forming production method.

Comparative Example 8

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 18 of Table 2, and then added into a crucible. The mixture was melted at 1550° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 650° C. at a rate of 360° C. per hour. After it was kept at 650° C. for 60 minutes, it was heated to 830° C. at a rate of 60° C. per hour. After it was kept at 830° C. for 30 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was white.

However, the glass was deformed during the crystallization heating process. Therefore, it was inadequate to be produced by the continuous forming production method.

Comparative Example 9

A mixture of glass raw materials was prepared according to the percentage composition as shown in sample 19 of Table 2, and then added into a crucible. The mixture was melted at 1580° C., and then formed into a 250 mm*250 mm*18 mm plate. After the glass plate was cooled, it was transferred to a heating furnace, kept at 200° C. for 10 minutes, and then heated to 700° C. at a rate of 120° C. per hour. After it was kept at 700° C. for 60 minutes, it was heated to 950° C. at a rate of 120° C. per hour. After it was kept at 950° C. for 120 minutes, it was cooled in the furnace.

As a result, a crystallized glass containing at least crystals of MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) was obtained. The appearance of the crystallized glass plate was nice and was beige.

However, the glass could not be crystallized in a short period of time. In addition, it was deformed and cracked during the crystallization heating process. Therefore, no product was obtained.

Table 1 and Table 2 show the percentage composition, crystal phase, crystal growth temperature/time, mechanical strength, color, thermal expansion coefficient, acid resistance, and alkali resistance of the samples of examples 1-10 and comparative examples 1-9.

The crystal phases A-I recited in Tables 1 and 2 indicate the following crystals, respectively:

A: Ca(Mg,Al)(Si,Al)₂O₆ (diopside)

B: MgSiO₃ (enstatite)

C: MgSiO₃ (clinoenstatite)

D: KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite)

E: K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T)

F: K(Si₃Al)O₈ (sanidine)

G: KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M)

H: KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1)

I: KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M)

Here the type of crystal is evaluated by x-ray diffraction.

The mechanical strength is determined by three-point bending strength testing device.

The color is evaluated by visual inspection.

As for the thermal expansion coefficient, a crystallized glass sample sized 20 mm*5 mm*5 mm is used for measuring the average coefficient of linear thermal expansion within a range of 30-400° C.

A crystallized glass sample sized 1.5 mm*1.5 mm*10 mm is immersed in 1% H₂SO₄ or 1% NaOH for 650 hours at 25, and then its weight loss (by mass percent) is used to determine its acid resistance and alkali resistance.

The tests on mechanical strength, thermal expansion coefficient, acid resistance and alkali resistance are not performed on the samples cracked or broken during the crystallization heating process.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Sample No. 1 2 3 4 5 6 7 8 9 10 SiO₂ 59.6 57.1 56.6 56.6 60.8 63.8 59.4 56.3 59.6 61.2 Al₂O₃ 11.4 11.4 11.4 11.4 11.9 11.9 11.4 8.3 11.4 14.0 MgO 11.4 11.4 14.4 11.4 14.4 11.4 13.6 19.8 13.3 11.0 CaO 3.5 6.0 3.5 3.5 3.5 3.5 1.5 1.5 3.5 4.0 Li₂O 1.7 1.7 1.7 1.7 1.2 1.2 1.7 1.7 1.7 1.2 Na₂O 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 1.1 3.0 K₂O 3.7 3.7 3.7 3.7 2.6 2.6 3.7 3.7 3.7 2.6 F 2.5 2.5 2.5 2.5 1.8 1.8 2.5 2.5 2.5 1.8 BaO 2.0 2.0 2.0 5.0 0.0 0.0 2.0 2.0 2.0 0.0 P₂O₅ 0.07 0.07 0.07 0.07 0.05 0.05 0.07 0.07 0.07 0.07 Rb₂O 0.66 0.66 0.66 0.66 0.46 0.46 0.66 0.66 0.66 0.66 Cs₂O 0.10 0.10 0.10 1.10 0.07 0.07 0.10 0.10 0.10 0.10 MnO₂ 0.23 0.23 0.23 0.23 0.14 0.14 0.23 0.23 0.23 0.23 Fe₂O₃ 0.14 0.14 0.14 0.14 0.08 0.08 0.14 0.14 0.14 0.14 Crystal A, B, C, A, B, C, A, B, C, A, B, C, A, B, C, A, B, C, A, B, C, B, C, E, A, B, C, A, B, C, phase E, F, G, D, E, D, E, E, F, E, F, E, F, E, F, F, G, E, F, F, G, H, I H, I F, G, H, I F, G, H, I G, H, I G, H, I G, H, I G, H, I H, I G, H, I Crystal 860° C. 860° C. 860° C. 860° C. 900° C. 900° C. 920° C. 875° C. 810° C. 910° C. growth 30 min. 60 min. 60 min. 30 min. 30 min. 60 min. 30 min. 60 min. 30 min. 30 min. temp./time Mechanical 631 946 767 773 702 708 530 669 500 520 strength (kg/cm²) Color white white white white white white white white white white Thermal 82 85 89 88 92 90 89 93 88 90 expansion coefficient* 10⁻⁷/° C. (30-400° C.) Acid 0.01 0.03 0.02 0.01 0.01 0.01 0.01 0.03 0.01 0.03 resistance (mass %) Alkali 0.02 0.01 0.01 0.02 0.01 0.01 0.03 0.03 0.04 0.02 resistance (mass %)

TABLE 2 Compar. Compar. Compar. Compar. Compar. Compar. Compar. Compar. Compar. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Sample No. 11 12 13 14 15 16 17 18 19 SiO₂ 52.2 67.1 64.6 60.7 63.6 58.8 59.1 58.8 59.4 Al₂O₃ 11.4 8.0 7.5 14.4 11.0 11.4 11.4 11.4 11.4 MgO 18.3 14.0 11.5 11.0 9.0 13.3 11.4 11.4 13.3 CaO 1.5 1.5 4.0 1.5 4.0 3.5 3.5 3.5 0.7 Li₂O 1.7 1.2 1.2 1.2 1.2 2.5 1.7 1.7 1.7 Na₂O 3.0 3.0 3.0 3.0 3.0 1.1 3.5 3.0 1.1 K₂O 3.7 2.6 2.6 2.6 2.6 3.7 3.7 4.5 3.7 F 2.0 1.8 1.8 1.8 1.8 2.5 2.5 2.5 2.5 BaO 5.0 0.0 3.0 3.0 3.0 2.0 2.0 2.0 5.0 P₂O₅ 0.07 0.05 0.05 0.05 0.05 0.07 0.07 0.07 0.07 Rb₂O 0.66 0.44 0.44 0.44 0.44 0.66 0.66 0.66 0.66 Cs₂O 0.10 0.07 0.07 0.07 0.07 0.10 0.10 0.10 0.10 MnO₂ 0.23 0.16 0.16 0.16 0.16 0.23 0.23 0.23 0.23 Fe₂O₃ 0.14 0.08 0.08 0.08 0.08 0.14 0.14 0.14 0.14 Crystal B, C, E, F, B, C, F, G, H, I A, B, C D B, C, F, G, H, I A, B, C, E, A, B, C, E, A, B, C, E, B, C, E, F, phase G, H, I F, G, H, I F, G, H, I F, G, H, I G, H, I β-spodumene Crystal 910° C. 880° C. 860° C. 980° C. 880° C. 860° C. 840° C. 830° C. 950° C. growth 30 min. 60 min. 60 min. 30 min. 30 min. 30 min. 30 min. 30 min. 120 min. temp./time mechanical 885 — — — — 530 650 680 — strength (kg/cm²) Color white white white white translucent white white white beige Thermal 91 — — — — 40 87 90 — expansion coefficient* 10⁻⁷/° C. (30-400° C.) Acid 0.035 — — — — 0.02 0.02 0.02 — resistance (mass %) Alkali 0.02 — — — — 0.03 0.01 0.01 — resistance (mass %)

As shown in Tables 1 and 2, the crystallized glass of the invention can be crystallized in a short period of time, have high mechanical strength, adequate thermal expansion coefficient that allows the crystallized glass to be used as a construction material, and good chemical durability. 

1. A MgO—Al₂O₃—SiO₂-based crystallizable glass, comprising, by mass percent, 55.0-65.0% SiO₂, 8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO, 1.0-2.2% Li₂O, 0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F.
 2. The crystallizable glass of claim 1, wherein lepidolite or a lithium-containing waste is used as a raw material for the crystallizable glass, wherein an amount of the lepidolite or the lithium-containing waste is 25-50% by mass of all raw materials used for the crystallizable glass, and the lepidolite or the lithium-containing waste comprises, by mass percent, 50.0-60.0% SiO₂, 20.0-30.0% Al₂O₃, 0-0.5% MgO, 3.0-5.0% Li₂O, 1.0-3.0% Na₂O, 6.0-9.0% K₂O, 4.0-6.0% F, 0-0.2% P₂O₅, 1.0-2.0% Rb₂O, 0.1-0.5% Cs₂O, 0.2-0.8% MnO₂, and 0.1-0.4% Fe₂O₃.
 3. A MgO—Al₂O₃—SiO₂-based crystallized glass, comprising, by mass percent, 55.0-65.0% SiO₂, 8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO, 1.0-2.2% Li₂O, 0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F.
 4. The crystallized glass of claim 3, comprising at least one or more crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M).
 5. The crystallized glass of claim 4, obtained by precipitating at least one or more crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) from the crystallizable glass of claim
 1. 6. The crystallized glass of claim 3, wherein lepidolite or a lithium-containing waste is used as a raw material for the crystallized glass, wherein an amount of the lepidolite or the lithium-containing waste is 25-50% by mass of all raw materials used for the crystallized glass, and the lepidolite or the lithium-containing waste comprises, by mass percent, 50.0-60.0% SiO₂, 20.0-30.0% Al₂O₃, 0-0.5% MgO, 3.0-5.0% Li₂O, 1.0-3.0% Na₂O, 6.0-9.0% K₂O, 4.0-6.0% F, 0-0.2% P₂O₅, 1.0-2.0% Rb₂O, 0.1-0.5% Cs₂O, 0.2-0.8% MnO₂, and 0.1-0.4% Fe₂O₃.
 7. The crystallized glass of claim 6, comprising at least one or more crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M).
 8. The crystallized glass of claim 7, obtained by precipitating at least one or more crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀ (lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂ (phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) from the crystallizable glass of claim
 1. 9. A method for manufacturing a MgO—Al₂O₃—SiO₂-based crystallizable glass, comprising: a step A, preparing a mixture of glass raw materials containing, by mass percent, 55.0-65.0% SiO₂, 8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO, 1.0-2.2% Li₂O, 0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F; a step B, melting the mixture obtained in the step A to give a melted glass; and a step C, shaping the melted glass obtained in the step B.
 10. The method of claim 9, wherein the step A comprises: a step A-1, stirring lepidolite or a lithium-containing waste, wherein the lepidolite or the lithium-containing waste contains, by mass percent, 50.0-60.0% SiO₂, 20.0-30.0% Al₂O₃, 0-0.5% MgO, 3.0-5.0% Li₂O, 1.0-3.0% Na₂O, 6.0-9.0% K₂O, 4.0-6.0% F, 0-0.2% P₂O₅, 1.0-2.0% Rb₂O, 0.1-0.5% Cs₂O, 0.2-0.8% MnO₂, and 0.1-0.4% Fe₂O₃; and a step A-2, preparing the mixture of glass raw materials by mixing, by stirring, the stirred product obtained in the step A-1 with other glass raw materials, wherein the stirred product is 20-50% by mass of the mixture of glass raw materials.
 11. A method for manufacturing a MgO—Al₂O₃—SiO₂-based crystallized glass, comprising: a step A, preparing a mixture of glass raw materials containing, by mass percent, 55.0-65.0% SiO₂, 8.0-14.0% Al₂O₃, 10.0-20.0% MgO, 1.5-6.0% CaO, 1.0-2.2% Li₂O, 0.7-3.0% Na₂O, 2.5-4.0% K₂O, and 1.5-3.0% F; a step B, melting the mixture obtained in the step A to give a melted glass; a step C, shaping the melted glass obtained in the step B to give a crystallizable glass; and a step D, performing a crystallization heating process on the crystallizable glass obtained in the step C.
 12. The method of claim 11, wherein the step A comprises: a step A-1, stirring lepidolite or a lithium-containing waste, wherein the lepidolite or the lithium-containing waste contains, by mass percent, 50.0-60.0% SiO₂, 20.0-30.0% Al₂O₃, 0-0.5% MgO, 3.0-5.0% Li₂O, 1.0-3.0% Na₂O, 6.0-9.0% K₂O, 4.0-6.0% F, 0-0.2% P₂O₅, 1.0-2.0% Rb₂O, 0.1-0.5% Cs₂O, 0.2-0.8% MnO₂, and 0.1-0.4% Fe₂O₃; and a step A-2, preparing the mixture of glass raw materials by mixing, by stirring, the stirred product obtained in the step A-1 with other glass raw materials, wherein the stirred product is 25-50% by mass of the mixture of glass raw materials.
 13. The method of claim 11, wherein the step D comprises precipitating at least one or more crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) by the crystallization heating process.
 14. The method of claim 12, wherein the step D comprises precipitating at least one or more crystals of Ca(Mg,Al)(Si,Al)₂O₆ (diopside), MgSiO₃ (enstatite), MgSiO₃ (clinoenstatite), KCa₄Si₈O₂₀(OH).8H₂O (hydroxyapophyllite), K(Li,Al)₃(Si,Al)₄O₁₀(lepidolite-3T), K(Si₃Al)O₈ (sanidine), KMg₃(Si₃Al)O₁₀(OH)₂ (biotite-1M), KMg₃(Si₃Al)O₁₀(OH)₂(phlogopite-2M1), and KAl₂Si₃AlO₁₀(OH)₂ (muscovite-1M) by the crystallization heating process. 